Dithiocarbazates and dithiocarbamates with acid and direct dyes

ABSTRACT

These dyes, notably for animal fibers, such as hair, wool, silk, and containing essentially acid or direct dyestuffs, comprise as adjuvants dithiocarbamic derivatives of formula: WHEREIN M is NH4, K or Na, and R1 and R2 identical or different represent each a hydrogen atom, a possibly substituted alkyl or phenyl, a NR3 (R4) group or a N=CR5 (R6) group, R1 and R2 being also able to form together and with the nitrogen atom to which they are linked a heterocycle. These adjuvants improve substantially the affinity of said dyestuffs for the fibers, consequently the intensity of the shade, as well as the uniformity of the dyeing.

United States Patent Galerne 5] Mar. 7, 1972 [72] Inventor:

[73] Assignee:

Jean Galeme, Paris, France Eugene-Callie, Societe Anonyme, Paris, France[221 Filed: Aug. 4, 1969 [21] Appl.No.: 847,436

[30] Foreign Application Priority Data Aug. 28, 1968 France ..164389[52] US. Cl ..8/l0, 8/40, 8/85, 8/172, 8/82 [51] Int. Cl. ..D06p 3/00[58] Field of Search ..8/l0, 10.1, 10.2, 85, 54,172, 8/82 [56]References Cited UNITED STATES PATENTS 2,116,521 5/1938 Kritchevsky..8/10.1 3,246,004 4/ 1966 Hall et a1. ..260/ 314.5

Ulrich et al. ..8/54 Ulrich et al. ..8/85

Primary Examiner-Donald Levy Attorney-Amster & Rothstein [57] ABSTRACTThese dyes, notably for animal fibers, such as hair, wool, silk, andcontaining essentially acid or direct dyestuffs, comprise as adjuvantsdithiocarbamic derivatives of formula:

dyestuffs for the fibres, consequently the intensity of th e shadeaswell as the uniformity of the dyeing.

2 Claims, No Drawings DITHIOCARBAZATES AND DITI-IIOCARBAMATES WITH ACIDAND DIRECT DYES DYES NOTABLY FOR ANIMAL FIBERS The present inventionrelates to dyes prepared from acid or direct dyestuffs.

According to the invention, these dyes are improved in that theycomprise as adjuvants dithiocarbamic derivatives of formula:

wherein M is NH,, K or Na, and R, and R are identical or different andrepresent each a hydrogen atom, a substituted or unsubstituted lower C,to C alkyl, a substituted or unsubstituted phenyl, a NR (R group,wherein R and R, are identical or difi'erent and represent each ahydrogen atom, a lower C, to C alkyl, a phenyl, or form together andwith the nitrogen atom to which they are linked. a. cycle. or an N =CR(R group wherein R and R,, are identical or different and represent eacha hydrogen atom, a lower C, to C alkyl, a phenyl, or form together acycle, the aforesaid radicals R, and R being also able to form togetherand with the nitrogen atom to which they are linked a cycle selectedamong the following wherein R, is a lower C, to C alkyl.

The substitutents of R, and R may be or comprise a dithiocarbamic group.

After exhaustive research the applicant found that the presence of theabove-defined dithiocarbamic derivatives as adjuvants in dyeing bathscontaining acid dyestuffs exerted a particularly favorable action. Thesedyeing baths used for coloring wool fibers in the form of tag wool, spunwool, fabric or any other form, have the property of dyeing thesematerials with considerably improved intensity and uniformity.

Comparative tests were actually performed on identical wool samples byutilizing the same dyeing bath compositions, the only differenceresiding in the presence, in one case, of one of the above-defineddithiocarbamic derivatives, the reference test being carried out underthe same time, pH and temperature conditions with a bath without anydithiocarbamic derivatives.

The dyestuff afi'mity is improved very considerably: thus, it wasobserved that the amount of fixed dyestuffs was up to five timesgreater.

The improved dyestuffs according to this invention have also beenutilized very successfully for dyeing keratinic fibers, notably humanhair, the dyestuffs used in this case being either direct or aciddyestuffs. Thus, new hair dyes have been developed, notably for humanhair. These products can be referred to as oxidation-free dyestufi's forbleached and nonbleached hair.

The addition of dithiocarbamic derivatives permits the use of direct andself-oxidizable dyestuffs warranting a maximum afiinity and insuring ashade uniformity which is definitely better than that obtained withhitherto known dyes.

The dyes according to this invention have the following generalcomposition, the percent values being given by weight for eachingredient:

0.05 percent to 0.3 percent of a conventional complexing agent foralkaline-earth ions and metallic ions in general, such as for instanceethylene-diaminotetracetic acid (sodium salt).

0.05 percent to 5 percent of a surface-active agent promoting thecontact between the dye and the fiber to be dyed, such as, for instance,oxyethylenated castor oil or sodium laurylsulfate.

0.05 percent to about 5 percent of a dyestuff for instance, such as PNfast blue in powder form (C.l. No.: acid blue 50), and JR Extra thioacidorange (C.I. No. 15,510).

1 percent to 5 percent of a dithiocarbamic derivative as definedhereinabove, such as, for instance, K, Na or NH, salt of morpholineN-dithiocarbamic acid, potassium dithiocarbazate and potassium N,N-diethyl dithiocarbamate.

balance to percent in the form of water or a mixture of water with ethylor benzyl alcohol.

ammonia or lactic acid, q.s. (quantity sufficient) for obtaining aneutral medium (pi-i=7), or ammonia, q.s. sufficient for obtaining analkaline medium (pl-I 7), as the dye may be neutral or alkalineaccording to the specific dyestuff utilized and the nature of the fiberto be dyed.

The dyes produced according to the present invention will thus containfrom about I percent to about 5 percent of the dithiocarbamic derivativeused as an adjuvant.

The dyes are prepared by simply mixing the various ingredients in thecold state, in any desired order, the solid components being dissolvedwithout any difficulty in the liquid components.

Thus, according to this invention, organic derivatives comprising one orseveral dithiocarbamic groups in their molecule are added to the dyeingbaths and the printing preparations generally employed for coloring woolin all possible forms thereof, and also silk.

These dithiocarbamic derivatives are also added to preparations used incapillary cosmetology for dyeing living hair. They are also suitable foruse in all operations consisting in dyeing natural or synthetic hair inthe wig-making art, in the manufacture of false hair, moustaches, etc.

Interesting results have also been achieved by adding these derivativesto baths intended for dyeing polyamids of all types, these bathscontaining the same acid dyestuffs as those utilized for dyeing wool.

The presence of dithiocarbamic derivatives permits, for a same finalresult, the use or more diluted dyeing baths, of dyestuffs which areknown to have as a rule little or no affinity for animal fibers, andalso of dyeing at a relatively low temperature if not at roomtemperature, a feature extremely advantageous in the case of certainfragile fibers, when a normal affmity is observed only at relativelyhigh temperature.

The invention will now be illustrated by reference to the followingexamples which however should not be construed as limiting the scope ofthe invention.

Examples Table l hereinafter shows dye formulations suitable for dyeingwool or silk or a polyamid such as Nylon 6-6 (Solutions A and B), or fordyeing human hair (Solutions C and D).

The percentages are given by weight.

5- Alkaline dye solution Chemical name Fo Ethylene diamino-tetraceticacid Potassium dithio- H2NN 'S K (sodium salt) carbazate. gOxycthylenated castor oil 2 5 Dyesmm (1) Potassium mo! ho-Dithiocarbarnic derivative (2) 3 li N.d1thi O N-C -S K Water balance to100 96 carboxylate. Ammonia q.s. to obtain pH=9 Potassium phenylldithiocarbamate. N H- fi- S K C- Dyeing of bleached hair S Potassiumpiperidine N-dithiocarboxyl- N -C S K Ethylene dinmino-tetracetic acidate. ll (sodium salt) 03% S Oxyethylenated castor oil 2 '11 l 5Potassium Hwdroxy Dyestuffs (l) 0.1% Dithiocarbamic derivative 2 9.5% gg g g gff" NH S K Water balance to I00 k S Ammonia q.s. to obtain pH=8Potassium i-sulfophenyl dithio- H0 S -NHC S K carbamate. II D- Dyeing ofnatural hair 8 sadiium gsgfigolpyl- CE; one- 0- Ethylenediammo-tetracetic acid 3 Na (sodium salt) 0.1% carbazate Oxyethylenatedcastor oil 2 CH S Dyemms (l) 0,11%) Potassium oyclo Dithiocarbamicderivative (2) 3 k Ammonium thioglycolm hexy1ldene-3 dithlo- C =N-NHfi-SK Water balance m 100 calbazate- S Ammonia q.s. to obtain pH=9 Ammoniumcyclopeutylidene-3 N -NH-C- S NH; quanmy mum! dithiocarbazete. g (i) seeTable ll Potassium dimethyl- CH (2) see Table III. 3,3 dithiocarbazate.N NH O s K CH S With each bath the dyeing operations have been camedout 1. at 20 C. Potassium methyl-3 C Hz-NH-NH- C- S K at 5 0dtthtocarbazate. ll. V 3. at 80 C, except for silk which would bedeteriorated. Potassium n-butyl- CHa-CHz OHi-CH-NHNHCs K In all casesthe dyeing time was 10 minutes. 3 dithmcarbamm' I Sodium phenyl-3 TABLEII dithiocarbazste. NHNH fi) S No Sodium henyl-3 DYESTUFF S 4 5 methy -3dithio- NNH C- 8 Na carbazate. I ll CH: S

Commercial Name Color index Number zg gggg g g HO CH3 CH2dithiocarbamate. N- C-- S K Fast blue "Powder Acid blue 50 $0 0 sSuli'acid orange JR Extra" 15 5 l0 Sulfacid bright pin]: 33" I00Ammonium N'- Sulfacid yellow "7 J" 47 035 methyl piperazine CHz-N N-C-SNR4 Sulfacid bright blue "1 J 42 080 i- 1| Sulfacid bright blue 2R H50"42 571 a Supracid black Lumiere RL" I7 580 Potassium N! CH8 Acetacid redR" 14 720 jgopro yl iper- Coriacid deep brown aziige fifihio- CH-N N-fi-S K car oxy 6.

CH 8 'osulfonated p-aminoo-diphcnylamine combined with the reactionproduct of resorcine with p-nitroaniline, the whole combined with themixture sult'onic Potassium fiq N NE S K nitroaminophenol-picramic acid(50 percentzSO percent by weight).

Potassium beuzyli- Chemical name Formula gggg g CHN NH |J S K PotassiumN N- 0H, S

dimethyl dithiocarbamate' N 0-3 K It was not possible to utilizepotassium 4-bydroxyphenyl dithiog H carbamate in a neutral medium due tothe insolubility in these a 3 conditions.

P CHgCHz M Y What i claim is: carbamate' N C S K l. A dye compositionwhich contains acid or direct C aC 2 dyestuffs and an adjuvantcomprising a composition of the for- Ptztassiuzfiidi- C H;( C H 4 mulaM11113 1 H NHC=S carbamate. N-C- S K N or a dithiocarbamic derivative ofthe formula wherein M is selected from the group consisting of NH K orNa, and R and R are selected from the group consisting of a hydrogenatom, a lower alkyl group having one to six carbon atoms, ahydroxy-substituted lower alkyl group containing one to six carbonatoms, a phenyl group, a hydroxy phenyl group, a phenyl sulfonic acidgroup, wherein only one of R, and R is a hydrogen atom a NR (R groupwherein R and R are selected from the group consisting of a hydrogenatom, a lower alkyl group having one to six carbon atoms, a phenyl groupor form together a cyclic radical a N C R (R group wherein R and R, areselected from the group consisting of a lower alkyl group having one tosix carbon atoms, and a phenyl group, or R and R, form a cyclic radicaltogether with the nitrogen atom to which they are linked said radicalbeing selected from the group consisting of

2. According to claim 1, enclosing said dithiocarbamic derivatives in an amount ranging from about 1 percent to about 5 percent by weight. 